CN107446898B - 一种可见光驱动的光敏剂-漆酶催化剂及其制备方法 - Google Patents

一种可见光驱动的光敏剂-漆酶催化剂及其制备方法 Download PDF

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CN107446898B
CN107446898B CN201710747675.6A CN201710747675A CN107446898B CN 107446898 B CN107446898 B CN 107446898B CN 201710747675 A CN201710747675 A CN 201710747675A CN 107446898 B CN107446898 B CN 107446898B
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杨建红
陈骏刚
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Abstract

本发明提供了一种可见光驱动的光敏剂‑漆酶催化剂及其制备方法。所述的光敏剂‑漆酶催化剂是一种钌多吡啶配合物光敏剂与漆树漆酶的共价结合物。该光敏剂‑漆酶催化剂按照以下方法制备得到的：将含氨基的钌多吡啶配合物光敏剂溶液与漆树漆酶溶液混合，然后加入N,N'‑二环己基碳二亚胺，反应后经凝胶色谱分离得到钌多吡啶配合物光敏剂与漆树漆酶的共价结合物。本发明所述光敏剂‑漆酶催化剂在可见光光照下，可有效降解水体中的有机污染物，催化降解效率高。

Description

一种可见光驱动的光敏剂-漆酶催化剂及其制备方法
技术领域
本发明是关于一种用于可见光驱动的光敏剂-漆酶催化剂及其制备方法，属于化学生物学领域。
背景技术
有效利用太阳能以驱动催化需要开发强大健全的系统，其中可以通过光照触发电子转移导致催化中心的活化的方式最终将光能转化为可储存的化学能；钌最外层具有4d75s1结构，其常见价态为Ru(Ⅰ)、Ru(Ⅱ)和Ru(Ⅲ)，并易于形成六配位的配合物，具有激发态反应活性高、寿命长、热力学稳定性好、光化学光物理信息丰富及发光性能好等特性，目前已有很多被广泛应用于非线性光学材料、化学发光、分子识别、分子光开关电子转移和光催化降解水及有机物等领域的研究。此外，联吡啶钌具有优异的的稳定性，对400～600nm的可见光有高效的吸收能力，已经广泛的应用于光催化反应的诸多领域。漆酶属于铜蓝氧化酶蛋白，能催化氧化多种难降解的有机污染物。目前，国内外对于漆酶降解水中有机污染物的研究开展了大量的工作，并将漆酶应用工业有机污水的治理，与其他方法相比，漆酶催化氧化法能耗低，易操作，降解效率高，使用范围广泛，是一项前景广阔的生物处理技术。而太阳光中大部分为可见光，因此发展在可见光范围内有响应的催化剂是十分必要的，近年来，可见光驱动催化降解引起了人们的广泛关注，具有工艺简单、能耗低、效率高、绿色无污染等特点，有广泛的应用前景。
发明内容
本发明主要是对可见光驱动催化降解进行研究，提供了一种相关的催化剂及其制备方法，使得钌多吡啶配合物光敏剂与漆树漆酶共价连接以增强在可见光范围内光驱动催化降解的效果。
本案发明人在研究中发现，可见光驱动催化降解中，激发光源对催化降解效果具有一定的影响，由于光敏剂在400～600nm的可见光有高效的吸收能力，激发光源能使光敏剂为激发态，以促进钌多吡啶配合物光敏剂与漆树漆酶之间的电子转移，能有效提高催化降解效果。
一方面，本发明提供了一种光敏剂-漆酶催化剂，其可用于可见光驱动催化降解方法，在可见光区域激发光源，增强催化降解效果。
根据本发明的具体实施方案，本发明的光敏剂-漆酶催化剂，包括一种钌多吡啶配合物光敏剂与漆树漆酶的共价结合物。
目前漆树漆酶作为生物催化剂在催化降解的应用，主要体现在对常见的酚类污染物的催化降解；现有的技术中尚未在可见光驱动催化降解领域发现漆树漆酶协同光敏剂通过可见光驱动增强催化降解效率的报道。本发明中将钌多吡啶配合物光敏剂与漆树漆酶的共价结合，用于可见光驱动催化降解，在可见光光照下，使光敏剂激发，增强催化降解的效果。
根据本发明的具体实施方案，本发明的光敏剂-漆酶催化剂中，所述的钌多吡啶配合物光敏剂与漆树漆酶的共价结合物是按照以下方法制备得到的：将钌多吡啶配合物光敏剂溶液与漆树漆酶溶液混合，向混合液中加入N,N'-二环己基碳二亚胺，反应后经凝胶色谱及透析得到钌多吡啶配合物光敏剂与漆树漆酶的共价结合物。
根据本发明的具体实施方案，本发明的钌多吡啶配合物光敏剂与漆树漆酶的共价结合物在制备时，钌多吡啶配合物光敏剂溶液与漆树漆酶溶液的混合，然后加入N,N'-二环己基碳二亚胺，在室温条件下反应2～6h，再经分离提纯即可。
根据本发明的具体实施方案，钌多吡啶配合物光敏剂与漆树漆酶的共价结合物制备时，含光敏剂的终浓度为1～10mg/L；漆酶的终浓度为10～1000mg/L；优选地，加入N,N'-二环己基碳二亚胺时的浓度为30～35mg/L。
根据本发明的具体实施方案，本发明的光敏剂-漆酶催化剂中，所述的光敏选用[Ru(bpy)2(PhenNH2)][PF6]2钌多吡啶配合物光敏剂。
根据本发明的具体实施方案，本发明的光敏剂-漆酶催化剂中，所述的漆酶选用漆树漆酶。
根据本发明的具体实施方案，本发明光敏剂-漆酶试剂为包括钌多吡啶配合物光敏剂与漆树漆酶的混合溶液。更具体地，制备时该溶液中，钌多吡啶配合物光敏剂优选为[Ru(bpy)2(PhenNH2)][PF6]2的终浓度为1～10mg/L；优选地，漆树漆酶在其溶液中的终浓度为 10～1000mg/L；进一步优选地，N,N'-二环己基碳二亚胺的浓度为30～35mg/L。
本发明的有意技术效果：
本发明通过加入N,N'-二环己基碳二亚胺，使钌多吡啶配合物光敏剂与漆树漆酶能形成光敏剂-漆酶共价结合物；
本发明在可见光光照条件下能提高催化降解的效率；
本发明的光敏剂-漆酶催化剂的制备方法简单易行，便于操作推广；
可多次催化降解，灵活配置催化降解方案。
附图说明
图1为钌多吡啶配合物光敏剂与漆树漆酶的共价结合物的紫外吸收光谱图。
具体实施方式
为了对本发明的技术方案、目的和效果有更加清楚的理解，现结合具体实施例以及附图对发明进行详细说明，应理解这些实施仅用于说明本发明而不用于限制本发明的范围。
实施例1：
[Ru(bpy)2(PhenNH2)][PF6]2钌多吡啶配合物光敏剂溶液(终浓度为5mg/L)与漆树漆酶溶液(终浓度为500mg/L)混合，并向该混合溶液中加入N,N'-二环己基碳二亚胺，使原混合溶液发生反应，放入的N,N'-二环己基碳二亚胺终浓度为30mg/L。
实施例2：
[Ru(bpy)2(PhenNH2)][PF6]2钌多吡啶配合物光敏剂溶液(终浓度为8mg/L)与漆树漆酶溶液 (终浓度为800mg/L)混合，并向该混合溶液中加入N,N'-二环己基碳二亚胺，使原混合溶液发生反应，放入的N,N'-二环己基碳二亚胺终浓度为33mg/L。
实施例3：
[Ru(bpy)2(PhenNH2)][PF6]2钌多吡啶配合物光敏剂溶液(终浓度为10mg/L)与漆树漆酶溶液(终浓度为100mg/L)混合，并向该混合溶液中加入N,N'-二环己基碳二亚胺，使原混合溶液发生反应，放入的N,N'-二环己基碳二亚胺终浓度为35mg/L。
图1为钌多吡啶配合物光敏剂与漆树漆酶的共价结合物的紫外吸收光谱图。可以看出在 400～475nm处有较高的吸收峰，这使得钌多吡啶配合物光敏剂与漆树漆酶能形成共价结合物更容易在可见光区域被激发，进而加快钌多吡啶配合物光敏剂与漆树漆酶之间的电子转移，提高对底物的催化降解的效率。

Claims (2)

1.一种光敏剂-漆酶催化剂，是由钌多吡啶配合物光敏剂[Ru(bpy)2(PhenNH2)][PF6]2与漆树漆酶经化学反应而制得的共价结合物。
2.权利要求1所述的光敏剂-漆酶催化剂，其制备方法为：
将浓度为1～10mg/L钌多吡啶配合物光敏剂溶液与浓度为1～1000mg/L的漆树漆酶溶液混合，然后加入30～35mg/L的N,N'-二环己基碳二亚胺，在室温条件下反应2～6h，再上Sephadex G-50层析柱，用0.1M、pH＝7.2的磷酸盐缓冲液洗脱分离，洗脱液装于透析袋中后置于蒸馏水中透析除去磷酸盐，最后透析袋内液经冷冻干燥得到共价连接的钌多吡啶配合物修饰的漆酶。
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CN101151764A (zh) * 2003-11-05 2008-03-26 圣路易斯大学 生物阴极中的固定化酶
US9290528B1 (en) * 2013-03-15 2016-03-22 University Of Kentucky Research Foundation Light-activated compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005093888A2 (en) * 2003-11-05 2005-10-06 St. Louis University Immobilized enzymes in biocathodes
CN101151764A (zh) * 2003-11-05 2008-03-26 圣路易斯大学 生物阴极中的固定化酶
US9290528B1 (en) * 2013-03-15 2016-03-22 University Of Kentucky Research Foundation Light-activated compounds

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* Cited by examiner, † Cited by third party
Title
argeting of photooxidative damage on single-stranded DNA representing the bcr-abl chimeric gene using oligonucleotide conjugates containing [Ru(phen)3]2-like photosensitiser groups;Conor W. Crean et al.;《Photochem. Photobiol. Sci.》;20021126;第1卷;第1024-1033页 *

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